Oligosaccharide-modified poly(propyleneimine) dendrimers: synthesis, structure determination, and Cu(II) complexation

The multiple application of reductive amination on primary amino groups of first and second generation poly(propyleneimine) dendrimers is used as a one-pot approach to introduce twice the amount of the oligosaccharide units as surface groups, compared to initially present amino groups in the first and second generation dendrimers. This was proven by (1)H NMR, MALDI-TOF-MS, and LILBID-MS analysis. The size of these dendrimers was determined by the hydrodynamic radius using pulsed field gradient NMR and dynamic light scattering. Molecular modeling confirmed the presence of dense-shell dendrimers. These dendrimers exhibit a generation dependent Cu(II)/dendrimer ratio in an aqueous environment, highlighting these materials as possible metal-carrier systems with a well-defined oligosaccharide protection shell for application in a biological environment.     

Nanoparticle-based immunosensors and immunoassays for aflatoxins

Aflatoxins are naturally existing mycotoxins produced mainly by Aspergillus flavus and Aspergillus parasiticus, present in a wide range of food and feed products. Because of their extremely high toxicity and carcinogenicity, strict control of maximum residue levels of aflatoxins in foodstuff is set by many countries. In daily routine, different chromatographic methods are used almost exclusively. As supplement, in several companies enzyme immunoassay-based sample testing as primary screening is performed. Recently, nanomaterials such as noble metal nanoparticles, magnetic particles, carbon nanomaterials, quantum dots, and silica nanomaterials are increasingly utilized for aflatoxin determination to improve the sensitivity and simplify the detection. They are employed either as supports for the immobilization of biomolecules or as electroactive or optical labels for signal transduction and amplification. Several nanoparticle-based electrochemical, piezoelectric, optical, and immunodipstick assays for aflatoxins have been developed. In this review, we summarize these recent advances and illustrate novel concepts and promising applications in the field of food safety.     

Novel aflatoxin derivatives and protein conjugates

Aflatoxins, a group of structurally related mycotoxins, are well known for their toxic and carcinogenic effects in humans and animals. Aflatoxin derivatives and protein conjugates are needed for diverse analytical applications. This work describes a reliable and fast synthesis of novel aflatoxin derivatives, purification by preparative HPLC and characterisation by ESI-MS and one- and two-dimensional NMR. Novel aflatoxin bovine serum albumin conjugates were prepared and characterised by UV absorption and MALDI-MS. These aflatoxin protein conjugates are potentially interesting as immunogens for the generation of aflatoxin selective antibodies with novel specificities.     

Nature’s Chemical Signatures in Human Olfaction: A Foodborne Perspective for Future Biotechnology

The biocatalytic production of flavor naturals that determine chemosensory percepts of foods and beverages is an ever challenging target for academic and industrial research. Advances in chemical trace analysis and post‐genomic progress at the chemistry–biology interface revealed odor qualities of nature’s chemosensory entities to be defined by odorant‐induced olfactory receptor activity patterns. Beyond traditional views, this review and meta‐analysis now shows characteristic ratios of only about 3 to 40 genuine key odorants for each food, from a group of about 230 out of circa 10 000 food volatiles. This suggests the foodborn stimulus space has co‐evolved with, and roughly match our circa 400 olfactory receptors as best natural agonists. This perspective gives insight into nature’s chemical signatures of smell, provides the chemical odor codes of more than 220 food samples, and beyond addresses industrial implications for producing recombinants that fully reconstruct the natural odor signatures for use in flavors and fragrances, fully immersive interactive virtual environments, or humanoid bioelectronic noses.     

Ultrafast energy-electron transfer cascade in a multichromophoric light-harvesting molecular square

A molecular square with dimensions of about 4 nm, incorporating sixteen pyrene chromophores attached to four ditopic bay-functionalized perylene bisimide chromophores, has been synthesized by coordination to four Pt(II) phosphine corner units and fully characterized via NMR spectroscopy and ESI-FTICR mass spectrometry. Steady-state and time-resolved emission as well as femtosecond transient absorption studies reveal the presence of a highly efficient (>90%) and fast photoinduced energy transfer (k(en) approximately equal to 5.0 x 10(9) s(-1)) from the pyrene to the perylene bisimide chromophores and a very fast and efficient electron transfer (>94%, k(et) approximately equal to 5 x 10(11) up to 43 x 10(11) s(-1)). Spectrotemporal parametrization indicates upper excited-state electron-transfer processes, various energy and electron-transfer pathways, and chromophoric heterogeneity. Temperature-dependent time-resolved emission spectroscopy has shown that the acceptor emission lifetime increases with decreasing temperature from which an electron-transfer barrier is obtained. The extremely fast electron-transfer processes (substantially faster and more efficient than in the free ligand) that are normally only observed in solid materials, together with the closely packed structure of 20 chromophoric units, indicate that we can consider the molecular square as a monodisperse nanoaggregate: a molecularly defined ensemble of chromophores that partly behaves like a solid material.     

Characterization of carotenoids and carotenoid esters in red pepper pods (Capsicum annuum L.) by high-performance liquid chromatography/atmospheric pressure chemical ionization mass spectrometry

Carotenoids and carotenoid esters were extracted from red pepper pods (Capsicum annuum L.) without saponification. Among the 42 compounds detected, 4 non-esterified, 11 mono- and 17 diesters were characterized based on their retention times, UV/Vis spectra and their fragmentation patterns in collision-induced dissociation experiments in atmospheric pressure chemical ionization mass spectrometry (APCI-MS). Positive and negative ion mode measurements were used for the characterization of major and minor carotenoids and their esters. Capsanthin esterified with lauric, palmitic and myristic acids represented the predominant compounds in the red pepper extracts. Additionally, three beta-cryptoxanthin and one zeaxanthin monoester were tentatively identified in red pepper pods for the first time. Furthermore, the specific fragmentation patterns of capsanthin-laurate-myristate and capsanthin-myristate-palmitate were used for the distinction of both regioisomers. The results obtained from LC-DAD-APCI-MSn experiments demonstrated that the carotenoid profile of red pepper pods is considerably more complex than considered hitherto.     

The moduli space of regular stable maps

We prove that the moduli space of regular stable maps in a complex manifold admits a natural complex orbifold structure. Our proof is based on Hardy decompositions and Fredholm intersection theory. The authors would like to thank the referee for his/her diligent work. We are grateful for the careful attention to detail in the report.     

Assessment of mitral regurgitation by magnetic resonance imaging

To evaluate the potential of magnetic resonance imaging (MRI) in detection and quantification of mitral regurgitation, 26 pts. with echocardiographically or angiographically documented mitral regurgitation were examined using a 0.5 Tesla superconducting magnet. In each patient a multislice-multiphase study in a sagittal-coronal double angulated projection (four-chamber view equivalent) was performed to assess left and right ventricular volumes, ejection fraction and regurgitant fraction. Additionally a blood flow sensitive cine-study (fast field echo: FFE) was done to visualize direction and area of regurgitant jet. MRI data were compared with quantitative and qualitative assessment of mitral regurgitation by angiography, 2D echocardiography, Doppler sonography and color flow mapping. Using the FFE mode MRI was able to detect the regurgitant jet as a typical signal loss within the left atrium in all patients. The ratio of regurgitant jet area/left atrium area as determined by MRI showed a correlation with a comparable ratio from color Doppler sonography of R = 0.87 (p < 0.001). There was also good agreement in semiquantitative grading of mitral regurgitation between MRI and angiography (R = 0.77, p < 0.001). The determination of left and right ventricular stroke volume allowed the calculation of the regurgitant fraction, which showed a correlation with invasively determined regurgitation fraction of R = 0.84 (p < 0.001). These data provide additional information that MRI may be useful as a noninvasive technique to detect and quantify mitral regurgitation.